Monoazo dyestuffs



United States Patent 3,215,686 MONOAZO DYESTUFFS Werner Zerweck and Richard Fleischhauer, Frankfurt am Main, and Heinz Bender, Bergen-Enkheim, Ifieis Hanan, Germany, assignors to Cassella Farbwerke Mainkur Aktiengesellschaft, Frankfurt am Main, e h m, Germany, a company f erm y No Drawing. Filed Jan. 21, 1963, Ser. No. 252,605 Claims priority, applicatigilGolermany, Jan. 22, 1962,

Q 1 Claim. (Cl. 260-162) This invention relates to new and valuable yellow monoazo dyestuffs having the formula in which X is a bivalent radical of the group consisting of S0 and Y is a radical of the group consisting of ethylene vinylene,

Z is a bivalent radical of the group consisting of S0 SO, 0 and S,

R is a substituent of the group consisting of a hydrogen atom and the radical R, R is a radical of the group consisting of alkyl, aryl, aralkyl and cycloalkyl, R" is a substituent of the group consisting of OH and R' is a substituent of the group consisting of a hydrogen atom, alkyl and aryl, R" is a radical of the group consisting of methyl, phenyl, carboxyl, carbamido and carbalkoxy, and n is an integer consisting of 0 and 1.

and

The new monoazo dyestuffs may be obtained by known coupling or acylating procedures, namely by coupling ,diazo compounds of arninophenylacylamines which may be further substituted in the phenyl residue and wherein the acylamino residue corresponds to the formula -.-IiI-.XY z

with pyrazols of the formula H. C C RIIII H II f F wherein X, Y, Z, R, R, R", R and R" have the fore- 3,215,686 Patented Nov. 2, 1965 "ice going meaning, or by acylating monoazo dyestuffs containing free amino groups instead of acylated amino groups with halides or anhydrides of organic acids containing the residue XYZR and by selecting the components in such a manner that the resultant dyestuffs contain not more than one sulfonic acid group.

The dyestuffs may be used for the'dyeing of animal, vegetable and synthetic fibers; they particularly distinguish themselves by yielding, when dyed or printed on cellulose fibers, dyeings and printings which are fast to washing, whereby they react in the form of their solutions or suspensions with these fibers in the presence of alkaline active agents especially at an elevated temperature or by dry heating.

On the one hand, the dyestulfs are resistant to alkaline active agents, and on the other hand, they may be fixed on the fiber with a good yield so that full dyeings and printings are obtained having very good wet fastness properties and a very good fastness to light.

The following examples are given for the purpose of illustrating the present invention. Where not otherwise stated, the temperatures given are in degrees centigrade.

Example 1 38.4 kg. 3-(fl-phenylsulfonylpropionylamino)-1-aminobenzene-6-sulfonic acid in the form of its sodium salt are dissolved in water, admixed with 6.9 kg. sodium nitrite and diazotized at 15-20 by allowing the mixture to run into ice and hydrochloric acid. The diazo suspension obtained is combined, in the presence of excess sodium acetate, With an aqueous suspension of about 10.3 kg. 3- methyl-S-pyrazolone. The dyestutf precipitated is filtered off and dried. It represents a yellow powder and it yelds on cotton, when printed in the presence of sodium carbonate, urea and alginate thickening and subsequently dried, steamed, rinsed and soaped, greenish yellow printings of a very good fastness to washing and light. The good fastness to light is retained even after crease-proof finishing.

E ample 2 24.2 kg. 1-amino-'3-( fl-methylsulfonylpropionylamino)- benzene are admixed, whilst stirring, with ice and hydrochloric acid and diazotized in the usual manner. The resultant diazo solution is introduced, in the presence of excess sodium acetate, into an aqueous solution of 26.7 kg. 1-(4-su1phophenyl)-3-methyl-5-pyrazolone. The dyestuff thus obtained is precipitated with potassium chloride, filtered off and dried. It forms a yellow water-soluble powder and yields, when applied on cotton as indicated in Example 1 or according to the padding process or to the cold pad batch dyeing method, yellow dyeings of a very good fastness to light and wet processing. The fixation is very good.

The before-mentioned dyestuffs may also be prepared by starting from the monoazo dyestulfs obtained by combining the diazo compounds of 3-nitro-1-aminobenzene or 3-acetylamino-l-aminobenzene with 1-(4-sulfophenyl)- 3-methyl-5-pyrazolone, by converting these monoazo dyestuffs by reduction or saponification into the aminoazo dyestulf and by acylating the latter in the presence of sodium bicarbonate with the chloride or anhydride of the IS-methylsulfonyl-propionic acid.

A dyestulf of similar properties, but of a more greenish The following table enumerates some further dyestufis which may be obtained according to the process of the present invention:

Dlazo component Coupling component Shade 3-methyl-5-pyrazolone Greenish yellow.

NH.O0.0H1.0Hfl-SO1OH$ a 0 Redd ls]: yellow.

NH.CO.CHz.CHg.SOz.CH3

| NH.CO.CH2.CH .SO .CH3

NH.CO.CH .CH2.SO .CH

I NH.OO.CHz.CH2.SOz.CHa

Nmooemomsomom 1 (2,5 diehloro 4' sulfophenyl) B-methylfi-pyrazolone.

1 (2 sulfophenyl) 3 phenyl 5 pytazolone.

1-(3-su1iophenyl)-3-methyl-5pyrazolone 5-pyrazolone-3-carboxyli e acid 1 (4 sulfophenyl) 5 pyrazolone Q 3 carboxylic acid ethyl ester.

1 (4 sulfophenyl) 5 pyrazol ene 3 carboxyhc acld.

Greenlsh yellow.

Reddlsh yellow.

Dlazo component Coupling component Shade SlOaH ONES SOaH ONE:

NH.C0.0Hz.CHz.SOz-

NH.CO.CHI.CH2.SO1CH3 NH.CO.CHz.CHg.SOzCH S0311 ONE:

NH.CO.CH:.CH:.SO3CH| SOaH nmcosmomoQ SOQH l ONE;

ONE:

l mmooomcmsQ 1-pl1enyl-5-pyrazolon-3-corboxyllc acid 5-pyraz01one 3-carboxylic acid 5-pyrazolone-3-carboxylic acid amide 3-methyl-5-pyrazolone I-phenyI-S-met hYI-E: pyrazolone 1- (3-chlorophenyl)-3-metliyl-5-pyrazolone.

3-methyl-l'z-pyrazolonm Yellow.

Reddish yellow.

Yellow.

Reddish yellow.

GreeniSh yellow.

Diazo component Coupling component Shad S 03H ONE; 3-methyl-5-pyrazo1one Gteenish yellow.

1 NELC O .CHz. CH2.S. C H

SlO H ONH2 do Do.

I NH. O 0. CH2. CH2.SO. 02H;

SlO H O-NHQ do Reddish yellow. NH.SOz. CH2. cmso-O NH: 1-(4-su1fopheny1)-3-methy1-5-prazo1one Yellow.

CH3 N C O.CH2.CHz.SO2. CzH5 NH, do I Greem'sh yellow.

0 O OH- I IH. 0 0.0112. CHa.SO2-

(I3 0 OH NH: do Do.

1110 0.0112. CH2.SO1O

-NH d0 D0.

01 1 IH.C O CH2. 0112.802. OH;

NH, .r1n Do.

I NELC O. CHmCHmSOnCHz NH: Yellow.

Diazo component Coupling component Shade 1(4-su1fophenyl)-pyrazolone-3-carboxylic acid. Reddish yellow.

l CH1. CH1 NC\ /CH2 CH2. CH:

0 ocmomsmQ IIIH:

. do D0.

G O CHzCHzSOaCHa w do .t Do.

. F O N C 0 CH2. CH2.SO2. CH

. d0 Yellow.

NH.CO.CHaCH2.SOz.CHr-C in which Y is a radical selected from the group consisting of ethylene and vinylene,

Z is a bivalent radical selected from the group consisting of S0 SO, and S,

R is a radical selected from the group consisting of lower alkyl, phenyl, and benzyl,

R" is a substituent selected from the group consisting of OH and H2,

45 R' is a substituent selected from the group consisting of hydrogen and phenyl,

R"" is a radical selected from the group consisting of methyl, phenyl, carboxyl, carbamido, and lower carbalkoxy,

50 n is an integer consisting of 0 and 1.

References Cited by the Examiner UNITED STATES PATENTS 1,594,867 8/26 Zitscher 260-162 X FOREIGN PATENTS 520,239 3/31 Germany.

CHARLES B. PARKER, Primary Examiner. 

